Polymeric magenta color former



Patented Mar. 2, 1954 POLYMERIC MAGENTA cocoa FORMER Sarah C. Kleiger and Henry J. Hugos, Binghamton, N. Y., assignors to General Aniline & Film Corporation, New York N. Y., a corporation of Delaware No Drawing. Application Deeember"27,'1Q5'0,

. iserialNo. 203,025

18 Claims. (Cl'. 957-6 This invention relates to the production or pbo czraphic dye mag b co r e m n and particularly to polymeric pyrazolones as coloreforming couplers therefor.

Modern methods of color photography utilize multilayer materials having differently sensitized superimposed silver halide emulsion layers, each containing color-forming components fast to diffusion which, upon development with a primary aromatic amino, developing agent, yield subtractively colored dyestufi images.

The magenta components most frequently employedare derivatives; which are ren dered fast to difiuslon by the inclusion of a suitable group which imparts a substantive character to the molecule of the component, or of a, long chain aliphatic hydrocarbon radical which nrevcnts difiusiqc at the. cqmpqnent the em l sion. 'Dye images. produced by such components are not entirely satisfactory. The principal disadvantage of these components is their generally waxy character which renders their purification extremely diificult, thus leading to, a loss in speed and contrast, undesired color shifts, and stain, The removal of the impurities which cause these undesirable photographic efiects is very timercqnsumiaa, exefinsive and. not always, very effective. I i

It has also been proposed to react pyrazolones with aliphatic aldehydes to yield dimeric or polymeric color formers. These too, sufier from the above shortcomings and have the added disadvanta e. of not being interchangeably compatible with; gelatin emulsions and other colloidal dispersions, such as modified polyvinyl alcohol which may; be used in place of gelatin as a colloidal carrier.

It. is an object of the present invention to provide a class of polymeric pyrazolone color formers for producing magenta dye images Another object is to provide photographic emulsions, containing, pqlymeria pyra olone; c9 9 formers capable-E yielding, upon: color development, dye images of excellent color, high brilllanceistability. and ery. fine grain,

A further object is to. provide photographic emulsions containing polymeric pyrazolones which do not afiect the sensitivity of photographic emulsions and do not cause stain.

Other objects and advantages of this invention will be apparent from the following specifications in which its preferred details and embodiments are described.

The above and other-objects are accomplished by the use of linear polymers obtained by condensing a dihalide Off a dioic acid with a l-substituted-3-aminopyrazolone to yield a bis-3-amidopyrazolone which is subsequently reacted with an aldehyde,

l t 2: wherein R is an; alkyl group, e. g., methyl, ethyl; propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, an aryl group, e. g;., phenyl, tolyl, methoxyphenyl, phenoxyphenyl, chlorophen-yl, nitrophenyl, naphthyl, an aralkyl group, a a, be li, ethalbe t en: ethyl, or a heterocyclic nucleus, e. g., thiazolyl, hen c'thiazqly quin01sl,, xridyl,and t e m B; is hydrogen or an alkyl, e. g., methyl, ethyl, prop b ts/l; isobut amyl, y hept-yl, ctyl. carbogryalkyl, e. g., carboxymethyl, carboxyethyl, carbqxypropyl, carboxybutyl, carboxyamyl, cycloalkyl, e. g., cyclopentyl, cyclohexyl, aryl, e. g., phenyl, tolyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyi, naphthyl, carboxyaryl, e. g., carboxyphenyl, carboxytolyl, carboxynaphthyl, sulfoaryl, e. g., sulfophenyl, sulfoto1yl, sulfonaphthyl, aralkyl, e .v g, benzyl, phenethyl and heterocyclic radicals, e. g., pyridyl, quinolyl, nicotenyl,

piperidyl, and wherein OC-ACO-. is a, di-

acyl radical of a dicarboxylic acid oi not more than 18 carbon atoms and selected from the class consisting of aliphatic, cycloaliphatic, aromatic, aromaticraliphatic, and heterocyclicdicarboxylic acids, e, g., oxalic, nalon-ic, succinic, glutaric, adipic, pimelic, suberic, azel'ai'c, sebacic, hendecanedioic, dodecanedioic, brassylic, tetradecanedioic, pentadecanedioic, thapsic, fumaric, glutaconic, a-hYdl'OlllllCOIlic, fi-hydromuconic, 2-octenedioic, phthalic, isophthalic, terephthalic, 2- methyl-1,4-benzenedicarboxylic, 2-methoxy-1,4- benzenedicarboxylic, 4,4'-dicarboxybiphenyl, 1,4- naphthalenedicarboxylic, 3-carboxylphenylacetyl, 3-carboxynaphthylacetyl, carboxycinnamic, carboxycyclohexaneacetic, camphoric, 1,4-cyclohexanedicarboxylic, pyrazolone dicarboxylic acid pyridinedicarboxylic and the like, which may be further substituted, for example, by alkyl, alkoxy and halogen, and X represents the number of repeated units in the polymer and is an integer greater than 2.

Examples of polymeric pyrazolones embraced Polymer of N.N'-bls-3-[l-phenyLS-pymzolonn]m-carboxycinnamicdiamide with formaldehyde Polymer of N.N'-b1s-3-[l-phenyl'fi-pyrazolonoJ-a'fi'GiethyI- succinamlde with formaldehyde 'one'molarequivalent of the dihalidei' of a. dioic condensingapproximatelytwomolar. e uivzflm ableldihalidesiof'dioic (dicarbo'Xylio) acid whioh 01" a, 1-subsfitut'ed'-3 amihopyrazolone"havihg' a may beused in'the preparation -orthe bisa;mld'o reactive methylene group" in" the" 4"-posit1o1r with py lon Carbonyl dichloride (phosgene) I Oxalyl chloride 60 Malonyl chloride Malonyl bromide Succinyl chloride Suocinyl bromide a, 8-Dimethy1succiny1 chloride 65 a,px-Diethy1succinyl chloride a,,B-Dibromosuccinyl bromide Glutaryl chloride Adipyl chloride acid" in the presence of a suitable soli'enf-diliterlt suclr as" pyridine, quino'line; orpicolin'e, a; high boiling aliphatic" amine such as" triethylamine or-tripropylamine; orin the presenceof dibxane which may contain a; small" amount ofan organic base such as-tfietliylmihe, and reactingthe resulting bis-amidbpyrazolone witli a email excess of s molar equivalent or an'- aldehyde iii the'pres ence of a solvent-diluent.

The preferred solvent-diluents for the polymerization of: the:bis amidopyrazolone with the aldehyde are dioxa-ne;pyridine;andldimethyl or' 21x32 33833: diethylacetamide. It ism bernoted; however; that Azelayl chloride solvent-diluents otherthan thosementioned sebacyl chloride above may also be employed; theweleetibn de- Hendecanedioyl hl rid pending. onttheeresistancerof thaseleeted diluent a-Butyl-a-ethylglutaryl chloride tomartioipatiomin: theweactiom 75 Dodecanedioyl chloride 15 Brassylyl chloride Tetradecanedioyl chloride Pentadecanedioyl chloride Thapsyl chloride Fumaryl chloride Glutaconyl chloride 2-hexenedioyl chloride 3-hexenedloyl chloride z-octenedioyl chloride 4-amyl-2,5-heptadienedioy1 chloride '7 2,9-dimethyl-2,4,6,8-decatetraenedioyl chlorid Hexadecanedioyl chloride Phthalyoyl chloride Isophthaloyl chloride Terephthaloyl chloride 2-methyl-1,4-benzenedicarboxyl chloride 2-methoxy-lA-benzenedicarboxyl chloride 1,4-naphthalenedicarboxyl chloride 3-carboxylcinnamoyl dichloride 3-carboxyldihydrocinnamoyl dichloride 3-carboxylphenylacetyl dichloride 3-carboxylnaphthylacetyl dichloride 4,4'-dicarboxyldiphenyl chloride 1,4-cyclohexanedicarboxyl chloride Camphoryl chloride (2-carboxyl-2-methylcyclohexane)acetyl dichloride 4,5-pyrazoledicarboxyl chloride 3,5-pyridinedicarboxyl chloride The following compounds are illustrative exam ples of suitable 3-amino-5-pyrazolones:

3-amino-l-phenyl-S-pyrazolone 3 -amino-1- (3 -methylphenyl) -5-pyrazolone 3-aminc-l- (4'-methoxyphenyl) -5-py1'azolone 3-amino- 1 (4'-phenoxyphenyl) -5-pyrazolone 3 amino 1 [4 (p. tert. butylphenoxy)- phenyl] 5 pyrazolone 3 amino 1 [4' (m tolyloxylphenyl] 5- pyrazolone v 3 amino 1 [4 (3,5" dimethylphenoxylphenyl] -5-pyrazolone 3-amino-1- [3 -chlorophenyl] -5-pyrazolone 3-amino-1- (4' nitrophenyl) -5-pyraz0lone B-amino-l- (2'-benzothiazolyl) -5-pyrazolone 3-amino-1- 1 -naphthyl) -5-pyrazolone 3-amino-l- (2'-naphthyl) -5-pyrazolone 3-amino-1-benzyl-5-pyrazolone 3-amino-l-phenethyl-5-pyrazolone 3-a-mino-1- (2-pyridyl) -5-pyrazolone S-amino-l- (2-quinolyl) -5-pyrazolone f1he-following are illustrative examples'of suitable aldehydes which may be utilized in the polymerization with the bis-amidopyrazolones:

Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde Iso-butyraldehyde Valeraldehyde Iso-Valeraldehyde Caproaldehyde Glyoxylic acid Formylacetic acid fi-Formylpropionic acid Formylsuccinic acid E-Formylcaproic acid Cyclopentanecarboxaldehyde Benzaldehyde l-naphthaldehyde o-Tolualdehyde m-Tolualdehyde p-Tolualdehyde "16 4-methoxybenzaldehyde 3-methoxybenzaldehyde 2-'methoxybenzaldehyde l-piperidine carboxaldhyd'e 2-pyridylpropionaldehyde Phenylacetaldehyde Phenylpropionaldehyde The polymeric pyrazolones prepared in accordance with the present invention are added to thesilver halide emulsion in the form of a solution or a suspension. in a suitable solvent such as an aqueous, alcoholic or -aqueous-alcoholic one normal solution of sodium or potassium hydroxide. Dispersing agents such as isopropylnaphthalene sulfonic acid or other suitable dispersing agents, for example, those disclosed .in United States Patent 2,186,717, may be used in preparing the suspensions of the polymeric pyrazolones for incorporation into silver halideemulsions. Instead of gelatin, the polymericpyrazolones may be' incorporated into other colloidal materials such as water dispersible organic esters of cellulose, polyamides, hydroxyethylcellulose, or modified polyvinyl. .alcohol.. The polymeric" pyrazolones have the unique property of being compatible not only with gelatinous silver halide emulsions but also with those which contain a synthetic colloidal carrier as a substitute for gelatin. 2'

As examples of suitable aromatic primary amino developing agents which maybe employed for the development of the color forming polymersof the present invention, there may be mentioned l-aminoaniline, 4-ethylaminoaniline, 2- diethylaminoaniline, l-dialkylaminoanilines, e. g., 4-dimethylaminoaniline, 4 diethylaminoaniline, 4- [N-fm-hydroxyethyl) -Nethyl] amin'oaniline, 4- 3,5 dihydroxyethyl) aminoaniline, 4 -amino-N- ylaniline sulfate and the like. These developing agentsarepreferably used in the form of their salts, such as the hydrochloride, since they are more soluble and stable than the free base. They are characterized by the presence of a free or primary amino group in the aromatic nucleus r Grams 4-'diethylaminoaniline hydrochloride 2 Sodium carbonate (anhydrous) '50 Sodium sulfite (anhydrous) 2 Potassium bromide 0.2 Water to make 1 liter.

The exposed silver halide emulsions containing the polymeric color-formersare developed inlth'e abovesoluti'onirrthe usual manner. Abl'a'ck and absorption maximum at 535 my. and" did not? white first developer and a: second exposure are show any indications of diffusibility'. The ma;- only employed: if the desiredv image is ta be: or genta image: was characterized by the fineness. the reversal type. of its grain, and showed greater than average- The invention is flurther illustrated; by the folistability on storage at elevated temperatures and lowing. examples, but it is to; be understood that high humidity as. well as: increased. resistance to the: invention not: to be restricted thereto; acid. fumes.

- Example II Polymer of N,N'-bis-3- [1-phenyl-5-pyrazolono]adipamide with formaldehyde Example I 42.5 grams (0.24 mole) of l-phenyl-d-amino- 1 5'-pyrazolone and 120 mls. of pyridine were H HOHN NH H:OH heated. together on a steam-bath. Te this mixture, 2'3 grams (0&125 mole) of adipyl chloride were. added dropwise with stirring. After 2 mixture was poured into 300 mls. of water. The precipitated: bis-amidopyrazolone was filtered; and first washed with water and then with dilute- Pelynrer ofi N,N'-bis-3- [.l-phenylL-fi-pyrazofono]urea with Mir-28kg formaldehyde: A mixtureconsisting. of 11.5 grams (0.025 mole)- 335 grams (0.05 mole) of 1-phenyl-3-amino-5- or. the dried bis-amidopyrazolone,y125- mls. of pyrazolone and. 25 mls. of pyridine were mixed dlOXaIle, 2 1 Of a formal-ill (0-025 111016)- I hours of continued stirring;' and heating... the

1 ammonia- The residue was dried and melted and warmed on a steam bath. 7.3 grams of. a. and 50 drops of pyridine Was t d un solution of phosgene in benzene. (containing 35 flux on a steam bath far hours- An additiflnall 2.56 grams or 0.025 mole of phosgene) were added Of ffl Was dd d in Order D dropwise tothe mixture. Heating and stirring vide a slight excess of formalin and eu were continued for an additional mmutes. continued for 1 hour. An insoluble p fld lfit Was- The reaction mixture was cooled to room tem-- filtered f the 11011 miXture a d Was ed perature. A White product separated which was 40 d 10 grams of the pr decomposing filtered ofi, washed with pyridine and dried in above 270 C. were obtained.

vacuo at room temperature using, concentrated A bright and t s magenta dy image sulfuric acid as a desiccant. The product can s a xi m abs p at 0 e Was p be further purified by recrystallization from hot duced by utilizing the above color former as in pyridine. The product decomposes when heated Ex ple I. The dye image Was Characterized above 260 C. by the fineness of its grain.

Example III X Polymer of N',N-bis-3-[I- (3'-toly1)-5-pyrazolono]adipamide with benzaldehyde-Z-sulfonic.afiid 1.87 grams (0.005 mole) of the above bis- 46 grams (0.24 mole) of 1-(3"-tolyl)-3'-aminoamidopyrazelene, 25 mls. of dioxane, 0.4 of S-pyrazolone and 120 mls. of pyridine were a 37% solution of. formalin (0.005 mole) and ten 00 heated together on a steam bath. To this mixdrops of pyridine were mixed. and refluxed for ture, 23 grams (0.125 mole) of adipyl chloride two hours. In order to provide a slight excess were added dropwise with stirring. After 2. hours of formaldehyde, 0.1 ml. of formalin was added of continued stirring and heating, the mixture at this point and the heating continued for an was poured into 300 mls. of Water. The preadditional 3 hours. The mixture was filtered (i5 cipitated .bis-amidopyrazolone was filtered, and

while hot and the residue washed with dioxane. first washed with water and then with dilute The yield of the dried material was 1.79 grams. ammonia, and subsequently dried. v i

0.35 gram of the above color former was dis-. A mixture of 11.9 grams (0.027 mole) of the persed in a small volume of dilute aqueous alkali dried bis-amidopyrazolone and 250 mls. of diand the dispersion added to 50 mls. of a gelatin oxane was heated on a steam bath. To this ous silver halide emulsion. The emulsion was mixture, 5 grams (0.028 mole) of the sodium salt coated onto a suitable support and dried. The. of benzaldehyde-Z-sulfonic acid and 50 drops of dried film was sensitometrically exposed and depyridine were added and the mixture was heated veloped in a 4-diethylaminoaniline developer. 'for dhcursonth'e steam gbath under refl'mi': The The brilliant magenta image obtained had an mixture was'filteredwh'ile hot and the filtrate 19 poured into approximately 1 liter of cold water. 77 grams (0.44 mole) of l-phenyl-3-amino-5'- The resultant solution was acidified by the addipyrazolone were mixed with 220 mls. of pyridine tion of hydrochloric acid until a polymerization and warmed on a steam bath with stirring. 53 product separated as a fine, tan-colored precipigrams (0.22 mole) of sebacyl chloride were added tate. 5 dropwise with stirring. Heating and stirring were The final product can be further purified by continued for 3 hours. After cooling, the mixture washing with hot ethanol. A bright and dense was poured into 500 mls. of cold water while magenta image was obtained by utilizing the stirring. The precipitated product was purified color former as in Example I. The dye image ,by stirring with dilute ammonia, washed with was characterized by the fineness of its grain. water and dried. Further purification can be ob- Ezample IV H-LCHGHNOCC C 0-NH(I}('3H-0H21OH t l C=o N \N Polymer of N,N-bis-3-[1- henyl-5-pyrazolono1terephthalamide wit formaldehyde 17.5 grams (0.1 mole) of 1-phenyl-3-amino tained by consecutive washings with alcohol and pyrazolone were dissolved in 60 mls. of hot pyriether. The'product melted at 251-3 C. dine and the solution heated to reflux. 10.3 2.1 grams (0.004 mole) of the bis-amidopyrazgrams (0.05 mole) of terephthalyl chloride disolone were dispersed in 25 mls. of dioxane, solved in 50 mls. of dioxane were added gradtreated with 0.4 ml. of 37% of formalin (0.15 ually to the boiling mixture. After the addition gram or 0.005 mole of formaldehyde) and 10 drops had been completed, refluxing was continued for of pyridine. The mixture was heated under reanother hour. The larger portion of the solvents flux on a steam bath for 5 hours. The solution present was then distilled off and the hot residue was filtered hot and poured into 100 mls. of water. poured into water. 7 A tarry product separated The finely divided product was made more readily which became granular upon acidification with filterable by the addition of hydrochloric acid. hydrochloric acid. The precipitate was filtered A magenta dye image of good density and brilofi, washed with water and dried in a vacuo over liance was obtained when the above color former concentrated sulfuric acid. The final product was utilized in the silver halide emulsion as in can be further purified by boiling out with hot Example I. The dye image obtained was charethanol. acterized by the fineness of its grain.

Ewample VI H (JHCHNOO(CH:)aGONHCCH--(EH- OH SOaH Polymer of N,N'-bis-3-[l-phenyl-E-pyrazolono]sebacamide with benzaldehyde-2-sulfonic acid 2.4 grams (0.005 mole) of the above bis-amido- 1 gram (0.0019 mole) of the bis-amidopyrazpyrazolone and 25 mls. of dioxane were mixed olone of Example V was mixed with 0.4 gram with 0.4 ml. formalin (containing 0.15 gram or (0.0019 mole) of the sodium salt of benzaldehyde- 0.005 mole of formaldehyde) and 10 drops of pyri- 2-sulfonic acid in 25 mls. of dioxane. The susdine. The mixture washeated for 4 hours on a pension was refluxed for 3 hours to yield a clear steam bath under reflux. The dioxane-insoluble light'brown solution. The solution was filtered fraction was filtered off and purified by washing and the filtrate diluted with 100 mls. of water to with dioxane. A bright and dense magneta dye give a milky suspension which was acidified with imag was produced by utilizing the above color hydrochloric acid, whereupon the polymer sepformer as in Example I. The dye image was aratedinafilterable form.

characterized by the fineness of its grain. A bright and dense magenta image was ob- ExampZeV H (|JH (|3-HNO C(CH2)8C 0NHC--CHCH::|OH

' o=o c=o Polymer of N,N'-bis-3-[i-phenyl-ii-pyrazolono]sebacamlde g with formaldehyde 7 .1,

tained when this polymeric color former was m corporated in a gelatin silver halide emulsiontas in Example I. It was particularly characterized by the fineness or: the" developed color grains.

Example VII 1 61 er whit nes 1* m a, a

0 witlrp'hdr xybgzaf hyd ple VI was remotes-with the exception: that h ydroxybenzaidehydo used in place or 0.4 gram (0.0019 more) or the sodium salt or henzaldehyde-flqultunic When a dispersion of this color former was-added to a silver halide emulsion, a magenta image of above average emery and fineness of grain was obtainea after'color-development.

Example 111 wherein R represents a member selected from the class consisting of alkyl, aryl, aralkyl and hetez 'ocyclic groups, R1 represents a member select'ed the class consisting or hydrogen;

some} simmido aiiz' i, m1, arallc rl and woman mamas,

wb -fio represents a radical of a ol carBoxy-Ho acid of not more than 18- carbonatoms and is selected from the class consisting of aliphatic, cycloaliphatic, aromatic, aliphaiti' aromatic; and heteroeyclie dicarboxylie acids, and- X represehts the mmilier of repeated: units the polymer and ism integer greatest-hair 2.

I Polymerpi NJV-bis B-[1 phonyl-5=pyraqolono-Isebacaiirl'de v I with fmtliafaldhyclic acid 2.1 grams (0.005 mole) of the sebacylamido bismyrazoloneoi Example V1,;25-mlar '01? diexa'rie, 10. drops of pyridine and. 0.15 grain. (0.005 mole). of phthalaldehydio acid were refluxed-for 5 hours to yield a dark brown. solutiom. The solution was. filtered while hot and the filtrate-poured into- 100 mls. of water. The finely divided precipitate-"was aggregatediby the addition of -'strong hydrochloric acid. The precipitate was filtered; washed with water, and dried in vacuo to'g-ive a light colored lowing formulae:

N N it i l 0 formaldehyde,

2. A. photographic silver halide eimlsioa cohtaming: as a: color former; theifioli mer or kiss s-{l1whenyi fi pyrazoiono l urea with; formaldehyde; r v

3-; a photographic silver halide mlfiim fiit taming as a color former, the polymer of NQN-" benza1dehyde-2-sulfonic acid. I w

i. A photographic saver-halide emulsion contailii flg as a color formerrtnepoiymer or Miif f' his 3 E 1 ph'eriyi' '5 pyrazomirolterephthah amide with fomiaidehycie;

5. A; ohotograohic silver halide emulsion con-"Q tainiiig as a color former, the olymer of NN bis-'3 E 1 -phenyl-5-pyrazol0no lsebacamidewith? 6; A nhotographiosilver" halide emulsion-con taming aaa color. formers the polymer of MN bis-B-l;hphenykE-pyrafiolonolsebacamide with.

phthalaldchydicvacid; 7, The method-cf? producing amagenta photographicimage a silver halide emulsion la er which comprises exposing thelayei an'erdeveiop mg it iwitira solution. of an aromatic primary ammo dwelofiihg agent, said emulsion Iay'er" eontaiifiirg as amagenta colorforiner, e; poly-r merit coaster compound or the class consisting of compounds "havii ig the folfowing general};

formulae hi -Z 23". andf wherein R represents a member selected from the class consisting oi alkyl, aryl, aralkyl, and

heterocyclic groups, R1 represents a member selected from the class consisting of hydrogen,

alkyl, cycloalkyl, aryl, aralkyl, and heterocyclic' radicals, OCA--CO represents a radical of a dicarboxylic acid of not more than 18 carbon atoms and is selected from the class consistingofaliphati -v cycloaliphatic, aromatic, aliphaticearomatic and heterocyclic dicarboxylic acids, and X represents thenumber of repeated units in the polymer and is an integer greater than2. Y 1 V 8. The method of producing a magenta photographic image in a silver halide emulsion layer which comprises exposingand developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolon0]urea with formaldehyde.

9. The method of producing a magenta'photographic image in a silver halide emulsion layer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing as a magenta color former, the polymer of N,N-bis-3- [1- (3-tolyl) -5-pyrazolono adipamide with benzaldehyde-Z-sulfonic acid.

. 10. The method of producing a magentaphotographic image in a'silver halide emulsion layer which comprises exposing and developingit with a solution of an aromatic primary amino de-.- veloping agent, said emulsion containing as a magenta color former, the polymer of N,N'-bis-3- [1 phenyl 5 pyrazolonolterephthalamide and formaldehyde. 1 g 1 11. The method of producing a magenta photographic image in a silver halide emulsion layer which comprises exposing and developing it with a solution of an aromatic primary amino-de-. veloping agent, said emulsion containing as a, ma genta color former, the polymer of N,N'-bis-3- [l phenyl-S-pyrazclono]sebacamide with form-' aldehyde.

12. The method of producing a magenta photographic image in a silver halide emulsionlayer which comprises exposing and developing it with a solution of an aromatic primary amino developing agent, said emulsion containing asa magenta color former, the polymer of N,N-bis- 3 [1 phenyl 5 pyrazolonolsebacamide with. phthalaldehydic acid.

. 13. A photographic element comprising a support and a -silver halide emulsion layer,-,said1 emulsion layer containing as a color iormerior the magenta image, a polymeric coupler compound of the classconsisting of compounds hav-. ing the following formulae: .7.

1 E saant enera r wherein R. represents a member selected from the class consisting of alkyl, aryl, aralkyl, and heterocyclic groups, R1 represents a. member selected from the class consisting of hydrogen, alkyl, carboxyalkyl, cycloalkyl, aryl, sulfoaryl, carboxyaryl, aralkyl, and heterocyclic radicals, and wherein OC-ACO-- represents a radical: ofsa dicarboxylicgacidr'oiLnot more than 18 port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N'-bis-3- [1-(3-tolyl) -5-pyrazolonoladipamide with benzaldehyde-Z-sulfonic acid.

aldehydic acid.

16. A photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for 'themagenta image, the polymer of N,N'-bis-3- E l-phenyl-5-pyrazolono l terephthalamide with formaldehyde.

1'7. A photographic element comprising a support and a silver halide emulsion layer, said emulsion layer containing as a color former for themagenta image, the polymer of N,N'-bis-3- [1-phenyl-5-pyrazolonolsebacamide with formaldehyde.

18. A photographicelement comprising a sup port and a silver halide emulsion layer, said emulsion layer containing as a color former for the magenta image, the polymer of N,N-bis-3- [1-phenyl-5-pyrazolonolsebacamide with phthal- SARAH c. KLEIGER.

HENRY J. nuoos.

.References" Cited in the file of this patent UNITED STATES PA'IENTS Number Date 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A POLYMERIC COUPLER COMPOUND OF THE CLASS CONSISTING OF COMPOUNDS HAVING THE FOLLOWING FORMULAE: 